Patent GB-770410-A (GB)
Title: Bis(p-aminophenoxy) deriv?tives of aliphatic hydrocarbons
Inventor: RAISON CLIFFORD GORDON
Filed: 1953-10-26
Abstract: The invention comprises compounds of the general formula <FORM:0770410/IV(b)/1> and their acid addition salts in which R1 is an alkyl group of 2 to 4 carbon atoms substituted by at least one hydroxy group on a carbon atom other than that adjacent to the nitrogen, R2 is hydrogen, an alkyl group of 1 to 4 carbon atoms or an alkyl group of 2 to 4 carbon atoms substituted by at least one hydroxy group on a carbon atom other than that adjacent to the nitrogen atom and W is a polymethylene chain -(CH2)n- or -CH2-M-CH2-, in which n is an integer from 2 to 10 and m is an aliphatic chain of 2 to 8 carbon atoms having one or more double or triple bonds, such bonds not being adjacent in the case where more than one are present. The compounds may be prepared by (1) reacting an a  : o -disubstituted compound of the formula X-W-X with a substituted phenyl compound of the formula <FORM:0770410/IV(b)/2> in which X and Y are radicals capable of reacting together to form an ether linkage and Z may be the group -NR1R2, when the latter is a tertiary amino group, or is a group capable of conversion to the group NR1R2, e.g. an acyl or nitroso group removed by hydrolysis or reduction respectively, and converting the group Z in the resulting bis-phenoxy compound as stated; (2) reacting the corresponding primary amine <FORM:0770410/IV(b)/3> with a compound R1B where B is a halogen or a sulphonic acid ester group, to give the corresponding secondary amines or the tertiary amines in which R2 is the same as R1; (3) where R1 and R2 are different, reacting the primary amine II first with a compound R1B and then with a compound R2B to give the tertiary amine; (4) reacting a primary amine of the formula II with an ethylene oxide derivative of the formula <FORM:0770410/IV(b)/4> to give products in which R1 or both R1 and R2 have the formula -CH2.CHOH.R3 (R3 being the remainder of the desired group) and (5) condensing a primary amine of the formula II with a halogenoalkyl chloroformate ester ClCOOR4Hal, in which R4 is an alkylene chain of 2 or 3 carbon atoms each of which may carry a methyl group as a substituent and Hal is a chlorine or bromine atom, followed by alkaline hydrolysis of the resulting intermediate cyclic compound. Examples describe the preparation of free bases or salts of compounds of the general formula I in which R1 is b -hydroxy ethyl, R2 is hydrogen and W is derived from propane, butane, pentane, hexane, heptane, octane, nonane, decane, but-2-ene, hex-3-ene and but-2-yne; R1 is b -hydroxyethyl, R2 is b -hydroxyethyl and W is derived from ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, but-2-ene, hex-3-ene, hept-3-ene, hexa-2 : 4-diene and but-2-yne; R1 is b -hydroxyethyl, R2 is methyl and W is derived from pentane, hexane, heptane, octane but-2-ene and but-2-yne, R1 is g -hydroxypropyl, R2 is hydrogen and W is derived from butane, pentane, hexane, heptane, and octane; R1 is b -hydroxyisopropyl, R2 is hydrogen and W is derived from hexane, heptane and octane; R1 is b -hydroxy-n-propyl, R2 is hydrogen and W is derived from but-2-ene; R1 is b -hydroxy-n-propyl, R2 is b -hydroxy-n-propyl and W is derived from hexane, heptane, octane, butane and pentane and R1 is b  : g -dihydroxypropyl, R2 is hydrogen and W is derived from heptane.  a  : o  - Bis (p - chloroalkoxycarbonamidophenoxy) alkanes and alkenes, used as intermediates in the preparation of compounds of the formula I, i.e. 1 : 5-bis-(p-b -chloroethoxycarbonamidophenoxy) pentane, 1 : 7-bis (p-g -chloropropoxycarbonamidophenoxy) heptane, 1 : 6-bis (p-b -chloroisopropoxycarbonamidophenoxy) hexane, 1 : 4 - bis - (p - b  - chloroethoxycarbonamidophenoxy) but-2-ene, 1 : 4-bis (p - b  - hydroxy - n - propylaminophenoxy) but-2-ene and 1 : 6-bis - (p - b  - chloroethoxycarbonamidophenoxy) hex-3-ene are made by treating the corresponding 1 : 6-bis (p-aminophenoxy) alkane or alkene with the appropriate chloroalkyl chloroformate.  1 : 4 - Bis - (p - b  - hydroxyethyl - N - nitrosoaminophenoxy) but-2-yne is made by treating p - b  - hydroxyethyl - N - nitrosoaminophenol with 1 : 4-dichlorobut-2-yne.  1 : 5 - Bis - (p - [tetrahydro - oxazol - 2 - one - 3 - yl] phenoxy) pentane is obtained by heating 1 : 5 - bis - (p - chloroethoxycarbonamidophenoxy) pentane with potassium hydroxide in aqueous alcohol; further hydrolysis of this with aqueous sodium hydroxide gives 1 : 5-bis-(p-hydroxyethylaminophenoxy)pentane. Specifications 749,907, 749,923, 758,382 and 765,957 are referred to.